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  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/755—Nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/007—Mixed salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
  • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
  • C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
  • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
  • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
  • C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
  • C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
  • C01B3/40—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts characterised by the catalyst
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/005—Spinels
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/391—Physical properties of the active metal ingredient
  • B01J35/392—Metal surface area
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
  • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
  • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/10—Catalysts for performing the hydrogen forming reactions
  • C01B2203/1041—Composition of the catalyst
  • C01B2203/1047—Group VIII metal catalysts
  • C01B2203/1052—Nickel or cobalt catalysts
  • C01B2203/1058—Nickel catalysts
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
  • C01B2203/1205—Composition of the feed
  • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
  • C01B2203/1235—Hydrocarbons
  • C01B2203/1241—Natural gas or methane
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the present invention relates to a nickel-based catalyst prepared using
• magnesium and aluminum in order to utilize nickel as an active metal and a
• hydrotalcite-like precursor consisting of aluminium and magnesium, which shows
• Hydrogen is a fundamental raw material for industrial application, and may be
• Hydrogen as a clean energy, is prepared mainly through a reforming reaction
• hydrocarbons such as natural gas, LPG, naphtha and gasoline.
• hydrogen may also be manufactured by gasification or electrolysis of fossil fuel and
• Examples of the reforming methods using fossil fuel include steam reforming,
• hydrocarbons has been known as a major cause of the deactivation of catalyst.
• the amount of the carbon deposition may be thermodynamically calculated from the hydrogen-carbon molar ratio and the oxygen-carbon molar ratio in
• hydrogen-carbon monoxide molar ratio may be produced because the water gas
• thermal stabilities such as an alumina support.
• Ni/Al 2 ⁇ 3 has been reported as a conventional catalyst for steam reforming
• zirconia-supported nickel catalyst prepared by adding cobalt to
• nickel is disclosed as a catalyst for steam reforming reaction of hydrocarbons [U.S.
• a promoter such as lanthanum, cerium and
• silver onto a general support such as alumina, silica, magnesia and zirconia is also
• manganese oxide and cerium oxide to an alumina support, followed by mixing a noble metal such as Pt, Pd, Rh and Ir, a transition metal such as Ni and Co and an
• alkaline earth metal such as Ca and Mg in an appropriate molar ratio, along with a
• This method also has the following problems that the production of catalyst is very
• multi-component catalyst reduce the usage of the noble metal, and improve the
• the catalyst showed 90% or higher conversion of methane only at 800 0 C
• catalysts showed 30% or lower conversion of methane except the catalyst containing
• nickel-based catalyst with highly dispersed nickel and higher specific surface area
• hydrotalcite-like catalyst precursor consisting of nickel, aluminum and magnesium
• hydrotalcite-like support through the substitution between nickel and magnesium
• the present invention may be accomplished by finding that hydrogen may be
• the present invention aims to provide a nickel catalyst with a highly reactive metal oxide.
• Figure 1 is a result of evaluating the stability for steam reforming of LPG over
• Figure 2 is a result of evaluating the stability for steam reforming of LPG over
• the present invention relates to a nickel-based catalyst for steam reforming
• x and y are molar ratios of Ni and Mg, respectively, relative to Al; x is
• the present invention relates to a process for steam reforming of LPG
• the present invention relates to a nickel-based catalyst prepared by optimizing the mixing ratio of nickel, aluminum and magnesium and using hydrotalcite-like
• the nickel-based catalyst prepared according to the conventional method has a
• the whisker carbon deposition usually contains
• hydrotalcite an anionic clay
• magnesium as a divalent metal and aluminum as a trivalent metal
• steam reforming reaction of methane or LPG is steam reforming of hydrocarbons.
• reaction temperature and a reaction pressure due to the difference of reactants i.e.
• methane is the most stable compound among
• hydrocarbons and requires a relatively higher temperature (above about 800 0 C) or higher pressure (above about 20 bars) for conversion of 85% or higher as compared
• hydrotalcite-like precursor is developed in the present invention by using hydrotalcite-like precursor. If the
• nickel content is above 24 wt%, nickel particles are large enough to promote the
• the nickel is below 10 wt%, the number of active sites for steam reforming reaction of
• the nickel-based catalyst herein forms 100-300 m 2 /g of specific
• the nickel-based catalyst having the aforementioned BET surface area having the aforementioned BET surface area
• the specific surface area of the active metal, nickel is maintained at the
• hydrotalcite-like precursor according to the present invention.
• hydrotalcite-like precursor examples include
• the present invention is prepared by adding an aluminum nitrate aqueous solution
• Al, x, is 0.25-1. If x is below 0.25, the activity of a catalyst may be lowered because
• the nickel content in the catalyst becomes lower than 10 wt% and active sites for the
• hydrotalcite-like precursor decreases and the catalytic activity may be lowered.
• x/y is 0.15-0.45. If x/y is below 0.15, hydrotalcite-like
• precursor may not completely formed and there may be presnt materials in the form
• the sodium carbonate serves as an anion for forming the
• hydrotalcite-like structure by stabilizing the brucite-type layers that divalent
• This solid is aged at 60-80 0 C for 12-18 hours to replace magnesium with nickel.
• the filtered precipitates are dried in a drying oven at 80-90 0 C
• the present invention is also characterized in that thus prepared
• nickel-based catalyst may be used in a steam reforming reaction of LPG to
• the steam reforming reaction of LPG is a
• the nickel-based catalyst As a pretreatment, the nickel-based catalyst
• a suitable amount of the catalyst sieved is charged in the reactor, and
• steam and LPG are introduced into the reactor as reactants so that the steam-carbon in LPG molar ratio may be 1-4 : 1, preferably 2-3 : 1.
• the steam-carbon in LPG molar ratio may be 1-4 : 1, preferably 2-3 : 1.
• the temperature of the reactor is controlled to 600-850 °C by an electrical heater
• the gas is introduced into the reactor by controlling the space velocity to
• carbosphere column is used for gas separation.
• the present invention improves the catalytic activity to maintain high
• Ni(NOa) 2 -6H 2 O was dissolved in 15 mL of distilled water, and this aqueous
• the precipitated product was placed at 60 0 C for 12 hours to develop
• hydrotalcite-like precursor was calcined at 850 0 C for 5 hours in
• nickel metal is highly dispersed on both the surface and the inner
• Nickel-based catalysts were prepared by following the same procedure as in
• Ni(NOs) 2 -OH 2 O were varied as presented in TABLE 1 while the amount of
• Nickel-based catalysts were prepared by following the same procedure as in
• Nickel-based catalysts were prepared by following the same procedure as in
• Al(NOs) 2 -9H2O were varied as presented in TABLE 3 while the amount of
• the ⁇ -Ab ⁇ 3 supported nickel catalysts were prepared according to an
• the MgO supported nickel catalysts were prepared according to an
• the specific surface area of the catalyst was 39.0 m 2 /g, and the surface
• the higher surface area of active nickel in the present invention appears to be due to
• Nickel-based catalysts were prepared with hydrotalcite-like precursor by
• nickel appears to be due to the fact that the support does not form a hydrotalcite-like
• molar ratio of steam to carbon in the propane gas may be 3 to 1.
• the space velocity was controlled to 10,000 Ir 1 based on
• reaction temperature 600 0 C to 850 0 C when steam
• the hydrogen selectivity was observed to be higher than 70% at 700 0 C in
• butane was performed on a catalyst with highest surface area and best activity
• nickel may be distributed in a highly uniform state on an improved hydrotalcite
• the conversion of reactant gas may be
• the steam-carbon molar ratio within 1 to 4, more preferably 2 to 3.
• Example 1 was subjected to the stability test as a function of reaction time at 800 0 C
• the hydrogen selectivity was 80% or higher until about
• the steam reforming reaction was performed same as in Example 1 except using
• methane as a reactant.
• 700, 750, 800 and 850 0 C were 3.5, 8.1, 32.1, 51.9, 81.5 and 93.8%, respectively, and the
• Example 3 was used, a mixture of propane and butane in a ratio of 30 : 70 as a
• Comparative Examples 6-7 compare the catalytic activity by performing
• methane was performed to improve the reforming reaction of methane by carbon
• hydrocarbons is performed on the same catalyst. It was also ascertained the nickel-based catalyst prepared using hydrotalcite-like precursor according to the
• present invention shows superior conversion of LPG and hydrogen selectivity in the
• Ni/ MgAl catalysts prepared using a hydrotalcite-like precursor according to the present invention, showed higher specific surface area of catalysts and surface area
• nickel-based catalysts prepared according to a conventional impregnation, which is
• hydrotalcite-like precursor generates hydrogen-rich gas for a long period of time in a
• processor for fuel cell or petroleum chemical process.

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• Organic Chemistry (AREA)
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• General Health & Medical Sciences (AREA)
• Combustion & Propulsion (AREA)
• Inorganic Chemistry (AREA)
• Hydrogen, Water And Hydrids (AREA)
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• 2005
  • 2005-10-20 KR KR1020050099208A patent/KR101300501B1/ko not_active IP Right Cessation
• 2006
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